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EP2338190A1 - Lithium ion battery - Google Patents

Lithium ion battery

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Publication number
EP2338190A1
EP2338190A1 EP09736241A EP09736241A EP2338190A1 EP 2338190 A1 EP2338190 A1 EP 2338190A1 EP 09736241 A EP09736241 A EP 09736241A EP 09736241 A EP09736241 A EP 09736241A EP 2338190 A1 EP2338190 A1 EP 2338190A1
Authority
EP
European Patent Office
Prior art keywords
layer
lithium
conducting
ion battery
membrane structure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP09736241A
Other languages
German (de)
French (fr)
Other versions
EP2338190B1 (en
Inventor
Otto Hauser
Hartmut Frey
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dritte Patentportfolio Beteiligungs GmbH and Co KG
Original Assignee
Dritte Patentportfolio Beteiligungs GmbH and Co KG
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Publication of EP2338190A1 publication Critical patent/EP2338190A1/en
Application granted granted Critical
Publication of EP2338190B1 publication Critical patent/EP2338190B1/en
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Lithium ion batteries essentially have three layers. One of the layers is the cathode layer, the other layer is the anode layer, and there is a film or membrane layer in between to separate the cathode and anode layers.
  • the cathode layer is composed of a metallic foil and a nanocrystalline layer applied thereto.
  • the nanocrystalline layer is selected from materials capable of storing metallic lithium. This storage is done either chemically or by depositing metallic lithium at the interface with the metallic electrode.
  • a well-known material for storing lithium ions is CoO 2 , which can intercalate and also release lithium ions.
  • the anode layer consists of nanocrystalline silicon or carbon. On the side remote from the cathode side, the anode layer is provided with a metallically conductive layer.
  • the membrane or film between these two layers is intended to electrically and mechanically isolate the cathode and the anode from each other. Only lithium ions can migrate through the film or membrane, ie, the intermediate layer between the cathode and the Anode layer is conducting lithium ions. The electrical conduction between the anode and the cathode layer takes place inside the lithium battery by lithium ions, the electrons flow in the load cell connected to the lithium battery or come from the power source when charging.
  • the LiCo0 2 molecules take up the lithium ions, resulting in a positively charged lithium atom and a free electron.
  • the electron flows via the anode terminal and the consumer to the cathode, while the positively charged lithium ion migrates through the Me ⁇ ibrane to the cathode.
  • the current flow direction is reversed, bringing the lithium ion with the electron at the anode back to the neutral lithium atom, which is incorporated into the anode layer.
  • PEO polyethylene oxide
  • the temperature resistance of the membrane between the electrodes is thus an essential determinant, which determines which maximum current the cell is charged with or at which current the cell can be maximally charged.
  • the charging process is the critical process, because charging the lithium battery is an exothermic process, so that the heating of the lithium battery is powered from the exothermic electrochemical process and the heat loss at the internal resistance of the lithium battery.
  • the higher the temperature resistance of the membrane the greater the charging currents can become, which in turn has a considerable influence on the charging time.
  • the new lithium battery has a multi-layered cathode.
  • the cathode has a metallically conductive layer and a polycrystalline layer deposited thereon.
  • the anode layer is also multi-layered and contains a polycrystalline layer and a metallically conductive layer.
  • the cathodes and the anode layer are separated from each other by a membrane structure having a higher temperature resistance than 150 0 C.
  • the two polycrystalline layers are nanocrystalline layers.
  • the metallic conductive layer of the cathode or the anode may be a nickel layer or a stainless steel layer.
  • the materials for the cathode layer can be made from Materials TiS 2 , MnO 2 , NiMn or CoO 2 are selected.
  • the materials for the anode layer can be selected from the substances C, Si, LiAl, LiC or LiNi.
  • nanocrystalline layers for the cathode and the anode is known. Any suitable method is suitable for this, for example ion beam mixing (ion beam mixing).
  • the ion conducting membrane structure may be one or two layers. In the case of the two-layer membrane, it is composed of a porous layer material and a layer which merely conducts lithium ions.
  • the lithium ion conductive layer is significantly thinner than the porous layer, which serves as a mechanical protection for the thinner lithium ion conductive layer.
  • the lithium-ion-conducting layer may be a layer which is initially impermeable immediately after application, also for lithium ions. Through appropriate physical treatment, this thin and initially impermeable layer will conduct lithium ions.
  • the layer is bombarded with lithium atoms or lithium ions, wherein the speed of the lithium ions is adjusted so that they either penetrate the membrane and leave channels, or largely penetrate the layer, but get stuck within the layer.
  • the remaining membrane thickness between the injected lithium atom and the corresponding electrode or the protective film layer should not be greater than 20 nm, while the film itself should have layer thicknesses between 10 and 20 ⁇ m. can point.
  • Another way to produce the membrane layer is to spray the base material for the polymer layer by means of high-pressure atomization in combination with ultrasonic atomization.
  • the polymer material is mixed with Li 3 PO 4 or Li 3 P or silicon nanoparticles.
  • a suitable method is described in DE 10 2008 047 955, which is incorporated herein by reference.
  • the desired polymerization occurs when the polymer material is sprayed into a high frequency plasma that is on the surface of the substrate.
  • polymers which have a glass transition temperature which is above 150 0 C.
  • polymers having a correspondingly high glass transition temperature, which per se are not lithium ions conductive can be made to become lithium ion conductive without their glass transition point changing unfavorably.
  • the gel electrolyte is based on star-shaped and linearly shaped polymer chains. Electrolyte in the structure of the GeI as a scaffold material may be incorporated again, the lithium ion is conductive and whose glass transition point is below 150 0 C. The mixture of the temperature-resistant framework with the low-melting material, which ensures the ionic conduction, a total of a membrane is produced, whose temperature resistance is above 150 0 C. Finally, a sol-gel layer can be applied by spin coating or dip coating. The sol-gel layer contains ZrO 2 particles, as well as H 3 PO 4 or Li 3 PO 4 . A sol-gel is a gel with a colloidal distribution of the solids in the liquid.
  • the figure shows the schematic structure of a lithium ion battery 1.
  • the lithium ion battery includes an anode assembly 2 and a likewise layered cathode arrangement 3. Between the anode and the cathode layer 2, 3 is a membrane structure layer 4, the anode layer 2 of the Cathode layer 3 separates to prevent an electrical short circuit between the two.
  • the cathode layer 3 is composed of a substrate 5 which is, for example, a nickel or an Inconel tape (stainless steel).
  • This band-shaped cathode layer 5 carries a polycrystalline layer 6 which is capable of accepting lithium ions in the crystal lattice, which the person skilled in the art refers to as intercalation.
  • the material for the polycrystalline layer 6 can be selected from the substances such as MnO 2 , COO 2 , MiMn or other substances with similar Interca- lation properties.
  • the polycrystalline layer 6 is applied to the substrate 5 by known methods, for example by Ion beam mixing, in which an ion beam is shot at a corresponding target, which consists of the material from which the nanocrystalline layer is to be generated.
  • the incident ions remove the material and transport it to the substrate 5, where it produces a corresponding nanocrystalline layer.
  • the 'diaphragm layer 4 is made up of two organic layers, with further below as to its construction and its production is further discussed.
  • the finally present on the Metnbran Anlagen 4 anode layer 2 is in turn composed of a polycrystalline layer 7 and a metallically conductive layer 8 together.
  • the polycrystalline layer 7 is made of a material selected from CSi, LiAl, LiC or LiNi. The material is chosen so that metallic lithium can be stored here.
  • polycrystalline layer 7 which is the active part of the anode layer 2
  • the application of the polycrystalline layer 7, which is the active part of the anode layer 2 can be done in the same way as explained above in connection with the layer ⁇ .
  • the layer 8 is applied by electroplating by chemical galvanization.
  • the layer 8 is, for example, "a metallic nickel layer.
  • the structure shown in the figure has a thickness between 30 microns and 100 microns.
  • the existing between the anode 2 and the cathode 3 Membrane layer 4 should on the one hand be conductive of lithium ions, but on the other hand should be sufficiently stable so that the membrane layer is not damaged during coating and subsequent operation.
  • the membrane layer 4 must be sufficiently temperature stable to maintain its mechanical and electrical properties as the cell heats up during operation.
  • the charging process is the more critical process, because the charging process is an exothermic process, so that the heat loss and the resulting heat in the chemical process add up.
  • the discharge process is an exothermic chemical process, with which the electrical waste heat is used up in part in the exothermic process, which helps to keep the temperature of the cell lower during the discharge process at the same current.
  • lithium ion conductive to mean a membrane which, in simple terms, works like a sieve and only allows lithium ions to pass other ions.
  • the membrane layer 2 is double-layered and is composed of a thin layer 11 and a thicker layer 12.
  • the thin layer 11 has a thickness of between 5 ⁇ m and 20 ⁇ m, while the thick layer has a thickness of between 10 and 20 ⁇ m.
  • the thick layer 12 is used for the manufacturing process of the lithium cell and should in the further manufacturing process, the thinner layer 11 from damage protect.
  • the thicker layer 12 is therefore "porous", ie it has passages that would not only allow lithium ions to pass through.
  • the thick layer 12 may, for example, consist of a poly sulfone film.
  • a polysulfone film would not be porous per se. To get it porous, it is stretched after the manufacturing process. This creates the desired through openings. Subsequently, the film thus obtained is applied, for example by calendering in a vacuum on the thin layer 12.
  • the important for the function of the lithium cell 1 layer 11 has a thickness of 2..5 microns.
  • the material for the layer 12 may be polysulfone, polybenzimidazole or polyphosphazene. This material, in itself, after being applied to the layer ⁇ , does not conduct lithium ions. In order to produce the desired ionic conductivity, the layer produced is bombarded with lithium ions or lithium atoms. As a result, the lithium ions or atoms penetrate into the layer 11 and generate the desired channels 13. It is not necessary that the channels 13 are broken through to the layer 6, it is sufficient if the lithium atoms as shown at 14, in the stuck sack-shaped channel 13. The distance between the bag-shaped end of the channel 13 and the layer 6 should be between 10 and 20 nm. Subsequent forming operation would drive lithium ions completely through the material of layer 11.
  • the lithium ion conductive layer or layer 11 of the membrane layer structure 4 produced in this way is subsequently heated by means of the layer 12, which is formed as explained above. is build, protected.
  • the above-mentioned base materials for the layer 11 of the membrane layer all have a gas transition temperature that is above 150 0 C, so that the proper operation of the lithium cell is guaranteed even at higher temperatures.
  • the lithium cell produced according to the invention thus allows a higher operating temperature than the lithium cells constructed with the prior art with PEO.
  • the batteries according to the invention can be charged correspondingly both during ' loading and unloading with larger currents.
  • the new lithium batteries are characterized by a lower internal resistance, since the "insulating" membrane between the anode and cathode is thinner than in the prior art.
  • the thickness of the membrane has an influence on the internal resistance. The smaller the thickness, the smaller the internal resistance of the cell, which in turn helps to minimize the heat loss during charging.
  • the lithiu ⁇ onen conductive layer 11 of the membrane layer 4 can also be produced, for example, by spraying the above-mentioned material with the addition of substances selected from the group Li 3 PO 4 , Li 3 P or silicon nanoparticles under high pressure on the layer 4.
  • the desired polymerization is carried out by the action of a high frequency plasma, on the sprayed material.
  • the embedded molecules later provide the desired channeling that allows the lithium ions to travel through.
  • a method for high pressure annealing is described for example in DE 10 2008 047 955. On this preliminary publication It is referred to here to avoid unnecessary repetition.
  • Another way to produce the ion-conducting layer 11 of the membrane layer 4 is to use a linked gel electrolyte consisting of star-shaped or linearly shaped polyeteketten.
  • This material forms a mechanical scaffolding that is mechanically sufficiently strong even at temperatures above 150 0C.
  • the interstices in the framework are filled by PEO, which is home-made by lithium ions.
  • the embedded PEO prevents the passage of other atoms, so that a membrane layer 4 is generated, which is only lithium ions conductive, even at temperatures above 150 0 C and thus at a temperature above the gas transition point of PEO.
  • the existing scaffold of the gel electrolyte prevents the liquefied PEO from disappearing locally and could cause a short circuit between the anode and the cathode.
  • Another way to produce the desired lithium ion conductive layer 11 is to create a membrane by depositing a saline gel layer. This is selected from the substances polybenimidazole or polyphosphazene in combination with ZrO 2 particles. This material is applied by spin coating or dip coating and then polymerized. The embedded zirconium dioxide molecules ensure that the corresponding lithium ion conductivity arises.
  • a lithium battery contains an anode and a cathode structure separated from each other by a membrane structure.
  • the membrane structure includes a layer that only lithium ions is conductive and is characterized by the property above the temperature 15O 1 0 C mechanically sufficiently firm to prevent a local short circuit between the anode and the cathode structure.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Separators (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

A lithium battery comprises an anode and a cathode structure which are separated from one another by a membrane structure. The membrane structure comprises a layer that only conducts lithium ions, said layer being characterized by the property of sufficient mechanical rigidity above the temperature of 150 °C to prevent a local short-circuit between the anode and the cathode structure.

Description

LithiujTtionen-Akku LithiujTtionen battery
Lithiumionen-Akkus weisen im Wesentlichen drei Schichten auf. Eine der Schichten ist die Kathodenschicht, die andere Schicht ist die Anodenschicht , und dazwischen befindet sich eine Folien- oder Membranschicht um die Kathoden- und Anodenschicht voneinander zu trennen.Lithium ion batteries essentially have three layers. One of the layers is the cathode layer, the other layer is the anode layer, and there is a film or membrane layer in between to separate the cathode and anode layers.
Die Kathodenschicht setzt sich aus einer metallischen Folie und einer darauf aufgebrachten nanokristallinen Schicht zusammen. Die nanokristalline Schicht ist aus Stoffen ausgewählt, die in der Lage sind metallisches Lithium zu speichern. Dieses Speichern geschieht entweder auf chemischem Wege oder durch abscheiden von metallischen Lithium an der Grenzfläche zu der metallischen Elektrode. Ein bekanntes Material zu Speichern von Lithiumionen ist CoO2, das Lithiumionen intercaieren und auch wieder abgeben kann.The cathode layer is composed of a metallic foil and a nanocrystalline layer applied thereto. The nanocrystalline layer is selected from materials capable of storing metallic lithium. This storage is done either chemically or by depositing metallic lithium at the interface with the metallic electrode. A well-known material for storing lithium ions is CoO 2 , which can intercalate and also release lithium ions.
Die Anodenschicht besteht aus nanokristallinem Silizium oder Kohlenstoff. Auf der von der Kathodenseite abliegenden Seite ist die Anodenschicht mit einer metallisch leitenden Schicht versehen.The anode layer consists of nanocrystalline silicon or carbon. On the side remote from the cathode side, the anode layer is provided with a metallically conductive layer.
Die zwischen diesen beiden Schichten befindliche Membrane oder Folie soll die Kathode und die Anode elektrisch und mechanisch voneinander isolieren. Es können lediglich Lithiumionen durch die Folie oder Membran hindurch wandern, d. h. die Zwischenschicht zwischen der Kathoden- und der Anodenschicht ist Lithiumionen leitend. Die elektrische Leitung zwischen der Anoden- und der Kathodenschicht geschieht im Inneren des Lithium-Akkus durch Lithiumionen, die Elektronen fließen im an den Lithium-Akku angeschlossenen Lastkreis oder kommen beim Laden aus der Spannungsquelle.The membrane or film between these two layers is intended to electrically and mechanically isolate the cathode and the anode from each other. Only lithium ions can migrate through the film or membrane, ie, the intermediate layer between the cathode and the Anode layer is conducting lithium ions. The electrical conduction between the anode and the cathode layer takes place inside the lithium battery by lithium ions, the electrons flow in the load cell connected to the lithium battery or come from the power source when charging.
Beim Entladevorgang nehmen die LiCo02-Moleküle die Lithiumionen auf, wodurch ein positiv geladenes Lithiumatom und ein freies Elektron entstehen. Das Elektron fließt über den Anodenanschluss und den Verbraucher zu der Kathode, während das positiv geladene Lithiumion durch die Meπibrane zur Kathode wandert. Beim Laden ist die Stromflussrichtung umgekehrt, womit sich das das Lithiumion mit dem Elektron an der Anode wieder zum neutralen Lithiumatom vereinigt, das in der Anodenschicht eingelagert wird.During the discharge process, the LiCo0 2 molecules take up the lithium ions, resulting in a positively charged lithium atom and a free electron. The electron flows via the anode terminal and the consumer to the cathode, while the positively charged lithium ion migrates through the Meπibrane to the cathode. When charging, the current flow direction is reversed, bringing the lithium ion with the electron at the anode back to the neutral lithium atom, which is incorporated into the anode layer.
Als Material für die Folie oder Membran wird bislang PEO (Polyethylenoxid) verwendet. Dieses Material ist bis ca. 150 0C hinreichend fest, um die gewünschte mechanische und elektrische Trennung zwischen den beiden Elektroden zu gewährleisten. Bei höheren Temperaturen verflüssigt sich das PEO zumindest lokal soweit, dass in diesem Bereichen Kurzschlüsse zwischen den beiden Elektroden stattfinden und die Zelle unbrauchbar wird.As the material for the film or membrane, PEO (polyethylene oxide) has heretofore been used. This material is sufficiently strong to about 150 0 C to ensure the desired mechanical and electrical separation between the two electrodes. At higher temperatures, the PEO liquefies at least locally so far that short circuits between the two electrodes take place in these areas and the cell becomes unusable.
Die Temperaturfestigkeit der Membrane zwischen den Elektroden ist somit eine wesentliche bestimmende Eigenschaft, die festlegt, mit welchem Strom die Zelle maximal belastet oder mit welchem Strom die Zelle maximal geladen werden kann. Dabei ist der Ladevorgang der kritischex'e Vorgang, denn das Laden des Lithium-Akkus ist ein exothermer Vorgang, so dass die Erwärmung des Lithium-Akkus gespeist wird, aus dem exothermen elektrochemischen Prozess und der Verlustwärme am Innenwiderstand des Lithium-Akkus. Je höher die Temperaturfestigkeit der Membrane ist, umso größer können die Ladeströme werden, was wiederum einen erheblichen Einfluss auf die Ladezeit hat.The temperature resistance of the membrane between the electrodes is thus an essential determinant, which determines which maximum current the cell is charged with or at which current the cell can be maximally charged. The charging process is the critical process, because charging the lithium battery is an exothermic process, so that the heating of the lithium battery is powered from the exothermic electrochemical process and the heat loss at the internal resistance of the lithium battery. The higher the temperature resistance of the membrane, the greater the charging currents can become, which in turn has a considerable influence on the charging time.
Ausgehend hiervon ist es Aufgabe der Erfindung ein Lithium-Akku zu schaffen, bei dem die Membrane eine größere Temperaturfestigkeit aufweist.Based on this, it is an object of the invention to provide a lithium battery, wherein the membrane has a greater temperature resistance.
Diese Aufgabe wird erfindungsgemäß durch einen Lithium-Akku mit den Merkmalen des Anspruches 1 gelöst.This object is achieved by a lithium battery with the features of claim 1.
Der neue Lithium-Akku weist eine mehrschichtige Kathode auf. Die Kathode weist eine metallisch leitende Schicht und eine darauf aufgebrachte polykristalline Schicht auf. Die Anodenschicht ist ebenfalls mehrschichtig und enthält eine polykristalline Schicht sowie eine metallisch leitende Schicht. Die Kathoden und die Anodenschicht sind voneinander durch eine Membranstruktur getrennt, die eine höhere Temperaturfestigkeit als 150 0C aufweist .The new lithium battery has a multi-layered cathode. The cathode has a metallically conductive layer and a polycrystalline layer deposited thereon. The anode layer is also multi-layered and contains a polycrystalline layer and a metallically conductive layer. The cathodes and the anode layer are separated from each other by a membrane structure having a higher temperature resistance than 150 0 C.
Vorzugsweise sind die beiden polykristallinen Schichten nanokristalline Schichten.Preferably, the two polycrystalline layers are nanocrystalline layers.
Die metallisch leitende Schicht der Kathode oder der Anode können eine Nickelschicht oder eine Edelstahlschicht sein. Diejenige metallisch leitende Schicht, die als letzte aufgebracht wird und insoweit nicht als Substrat dient, kann auf galvanischem Wege aufgetragen werden, während die andere Schicht als stabilisierendes Substrat dient.The metallic conductive layer of the cathode or the anode may be a nickel layer or a stainless steel layer. The metallically conductive layer, which is applied last and does not serve as a substrate insofar, can be applied by electroplating, while the other layer serves as a stabilizing substrate.
Die Materialien für die Kathodenschicht können aus den Stoffen TiS2, MnO2, NiMn oder CoO2 ausgewählt werden.The materials for the cathode layer can be made from Materials TiS 2 , MnO 2 , NiMn or CoO 2 are selected.
Die Materialien für die Anodenschicht können aus den Stoffen C, Si, LiAl, LiC oder LiNi aufgewählt werden.The materials for the anode layer can be selected from the substances C, Si, LiAl, LiC or LiNi.
Das aufbringen der nanokristallinen Schichten für die Kathode und die Anode ist bekannt. Es kommt hierzu jedes entsprechende Verfahren in Frage, wie beispielsweise Ionen- εtrahlbeschichtung (Ion-Beam-Mixing) .The application of the nanocrystalline layers for the cathode and the anode is known. Any suitable method is suitable for this, for example ion beam mixing (ion beam mixing).
Die Ionen leitende Membranstruktur kann ein oder zweischichtig sein. Im Falle der zweischichtigen Membrane setzt sie sich aus einem porösen Schichtmaterial und einer lediglich Lithiumionen leitenden Schicht zusammen. Die Lithiumionen leitende Schicht ist deutlich dünner als die poröse Schicht, die als mechanischer Schutz für die dünnere Lithiumionen leitende Schicht dient.The ion conducting membrane structure may be one or two layers. In the case of the two-layer membrane, it is composed of a porous layer material and a layer which merely conducts lithium ions. The lithium ion conductive layer is significantly thinner than the porous layer, which serves as a mechanical protection for the thinner lithium ion conductive layer.
Bei der Lithiumionen leitenden Schicht kann es sich um eine Schicht handeln, die unmittelbar nach dem Aufbringen zunächst undurchlässig ist, auch für Lithiumionen. Durch eine entsprechende physikalische Behandlung wird diese dünne und ursprünglich undurchlässige Schicht Lithiumionen leiten. Hierzu wird beispielsweise im Ionenstrahlverfahren die Schicht mit Lithiumatomen oder Lithiumionen beschossen, wobei die Geschwindigkeit der Lithiumionen so eingestellt wird, dass sie entweder die Membrane durchdringen und Kanäle hinterlassen, oder die Schicht weitgehend durchdringen, jedoch innerhalb der Schicht stecken bleiben. Die verbleibende Membranstärke zwischen dem eingeschossenen Lithium- atom und der entsprechenden Elektrode oder der schützenden Folienschicht sollte nicht größer als 20 nm sein, während die Folie selbst Schichtstärken zwischen 10 und 20 μm auf- weisen kann.The lithium-ion-conducting layer may be a layer which is initially impermeable immediately after application, also for lithium ions. Through appropriate physical treatment, this thin and initially impermeable layer will conduct lithium ions. For this purpose, for example, in the ion beam method, the layer is bombarded with lithium atoms or lithium ions, wherein the speed of the lithium ions is adjusted so that they either penetrate the membrane and leave channels, or largely penetrate the layer, but get stuck within the layer. The remaining membrane thickness between the injected lithium atom and the corresponding electrode or the protective film layer should not be greater than 20 nm, while the film itself should have layer thicknesses between 10 and 20 μm. can point.
Eine andere Möglichkeit die Membranschicht zu erzeugen, besteht darin das Grundmaterial für die Polymerschicht mittels Hochdruckverdüsung in Kombination mit Ultraschallvernebelung aufzusprühen. Dem Polymermaterial ist Li3PO4 oder Li3P oder Siliziumnanopartikel beigemischt. Ein geeignetes Verfahren ist in der DE 10 2008 047 955 beschrieben auf die hier Bezug genommen wird.Another way to produce the membrane layer is to spray the base material for the polymer layer by means of high-pressure atomization in combination with ultrasonic atomization. The polymer material is mixed with Li 3 PO 4 or Li 3 P or silicon nanoparticles. A suitable method is described in DE 10 2008 047 955, which is incorporated herein by reference.
Die gewünschte Polymerisation findet statt, wenn das Polymermaterial in ein Hochfreguenzplasma hinein gesprüht wird, dass sich auf der Oberfläche des Substrates befindet.The desired polymerization occurs when the polymer material is sprayed into a high frequency plasma that is on the surface of the substrate.
In jedem Falle werden Polymere verwendet, die eine Glasumwandlungstemperatur haben, die über 150 0C liegt. Durch die beschriebenen Verfahren können Polymere mit einer entsprechend hohen Glasumwandlungstemperatur, die an sich nicht Lithiumionen leitend sind, dazu gebracht werden Lithiumionen-leitend werden, ohne dass ihr Glasumwandlungs- punkt sich in ungünstiger Weise verändert.In any case, polymers are used which have a glass transition temperature which is above 150 0 C. By virtue of the processes described, polymers having a correspondingly high glass transition temperature, which per se are not lithium ions conductive, can be made to become lithium ion conductive without their glass transition point changing unfavorably.
Eine weitere Möglichkeit die Membrane zu erzeugen, besteht darin einen kovalente verlinkten Gel-Elektrolyten zu verwenden. Der Gelelektrolyt basiert auf sternförmig und linear geformten Polymerketten. In die Struktur des GeI- elektrolyten als Gerüst kann wiederum Material eingelagert werden, das Lithiumionen leitend ist und dessen Glasumwandlungspunkt unterhalb von 150 0C liegt. Durch das Gemisch aus der temperaturfesten Gerüst mit dem niedrig schmelzenden Material, das die Ionenleitung gewährleistet, wird insgesamt eine Membran erzeugt, deren Temperaturfestigkeit über 150 0C liegt. Schließlich kann eine Sol-Gel-Schicht durch Spin- oder Dip-Coating aufgebracht werden. Die Sol-Gel-Schicht enthält ZrO2-Partikel, sowie H3PO4 oder Li3PO4. Bei einem Sol-Gel handelt es sich um ein Gel mit koloidaler Verteilung der Festkörper in der Flüssigkeit.Another way to create the membrane is to use a covalent linked gel electrolyte. The gel electrolyte is based on star-shaped and linearly shaped polymer chains. Electrolyte in the structure of the GeI as a scaffold material may be incorporated again, the lithium ion is conductive and whose glass transition point is below 150 0 C. The mixture of the temperature-resistant framework with the low-melting material, which ensures the ionic conduction, a total of a membrane is produced, whose temperature resistance is above 150 0 C. Finally, a sol-gel layer can be applied by spin coating or dip coating. The sol-gel layer contains ZrO 2 particles, as well as H 3 PO 4 or Li 3 PO 4 . A sol-gel is a gel with a colloidal distribution of the solids in the liquid.
In der einzigen Figur der Zeichnung ist der prinzipielle Aufbau des Lithiumionen-Akkus dargestellt. Die Zeichnung ist nicht maßstabsgerecht und plakativ vereinfacht, um das für die Erfindung wesentliche besser verstehen zu können.In the single figure of the drawing, the basic structure of the lithium ion battery is shown. The drawing is not to scale and simplistic simplified in order to understand the essential for the invention better.
Die Figur zeigt den schematisierten Aufbau eines Lithiumionen-Akkus 1. Zu dem Lithiumionen-Akku gehört eine Anodenanordnung 2 sowie eine ebenfalls schichtförmige Kathodenanordnung 3. Zwischen der Anoden- und der Kathodenschicht 2, 3 befindet sich eine Membranstrukturschicht 4, die die Anodenschicht 2 von der Kathodenschicht 3 trennt, um einen elektrischen Kurzschluss zwischen beiden zu verhindern.The figure shows the schematic structure of a lithium ion battery 1. The lithium ion battery includes an anode assembly 2 and a likewise layered cathode arrangement 3. Between the anode and the cathode layer 2, 3 is a membrane structure layer 4, the anode layer 2 of the Cathode layer 3 separates to prevent an electrical short circuit between the two.
Die Kathodenschicht 3 setzt sich aus einem Substrat 5 zusammen, das beispielsweise ein Nickel- oder ein Inconel- band (rostfreier Edelstahl) ist. Diese bandfömige Kathodenschicht 5 trägt eine polykristalline Schicht 6, die in der Lage ist Lithiumionen im Kristallgitter aufzunehmen, was der Fachmann als Intercalation bezeichnet. Das Material für die polykristalline Schicht 6 kann aus den Stoffen wie MnO2, COO2, MiMn oder anderen Stoffen mit ähnlichen Interca- lationseigenschaften ausgewählt werden.The cathode layer 3 is composed of a substrate 5 which is, for example, a nickel or an Inconel tape (stainless steel). This band-shaped cathode layer 5 carries a polycrystalline layer 6 which is capable of accepting lithium ions in the crystal lattice, which the person skilled in the art refers to as intercalation. The material for the polycrystalline layer 6 can be selected from the substances such as MnO 2 , COO 2 , MiMn or other substances with similar Interca- lation properties.
Die polykristalline Schicht 6 wird auf das Substrat 5 durch bekannte Verfahren aufgetragen, beispielsweise mit- tels Ionenbeam-Mixing, bei dem ein Ionenstrahl auf ein entsprechendes Target geschossen wird, das aus dem Stoff besteht, aus dem die nanokristalline Schicht erzeugt werden soll. Die auftreffenden Ionen tragen das Material ab und transportieren es auf das Substrat 5, wo es eine entsprechende nanokristalline Schicht erzeugt.The polycrystalline layer 6 is applied to the substrate 5 by known methods, for example by Ion beam mixing, in which an ion beam is shot at a corresponding target, which consists of the material from which the nanocrystalline layer is to be generated. The incident ions remove the material and transport it to the substrate 5, where it produces a corresponding nanocrystalline layer.
Die 'Membranschicht 4 setzt sich aus zwei organischen Schichten zusammen, auf die weiter unten hinsichtlich, ihres Aufbaus und ihrer Erzeugung weiter eingegangen wird.The 'diaphragm layer 4 is made up of two organic layers, with further below as to its construction and its production is further discussed.
Die auf der Metnbranschicht 4 schließlich vorhandener Anodenschicht 2 setzt sich wiederum aus einer polykristallinen Schicht 7 und einer metallisch leitenden Schicht 8 zusammen. Die polykristallie Sschicht 7 besteht aus einem Material, das aus den Stoffen CSi, LiAl, LiC oder LiNi ausgewählt ist. Das Material ist so gewählt, dass hier metallisches Lithium eingelagert werden kann.The finally present on the Metnbranschicht 4 anode layer 2 is in turn composed of a polycrystalline layer 7 and a metallically conductive layer 8 together. The polycrystalline layer 7 is made of a material selected from CSi, LiAl, LiC or LiNi. The material is chosen so that metallic lithium can be stored here.
Das Aufbringen der polykristallinen Schicht 7, die den aktiven Teil der Anodenschicht 2 darstellt, kann in der gleichen Weise geschehen, wie dies zuvor in Verbindung mit der- Schicht β erläutert ist.The application of the polycrystalline layer 7, which is the active part of the anode layer 2, can be done in the same way as explained above in connection with the layer β.
Schließlich wird die Schicht 8 auf galvanischem Wege aufgetragen und zwar durch chemisches Galvanisieren. Die Schicht 8 ist beispielsweise " eine metallische Nickelschicht .Finally, the layer 8 is applied by electroplating by chemical galvanization. The layer 8 is, for example, "a metallic nickel layer.
Insgesamt hat der in der Figur dargestellte Aufbau eine Dicke zwischen 30 μm und 100 μm.Overall, the structure shown in the figure has a thickness between 30 microns and 100 microns.
Die zwischen der Anode 2 und der Kathode 3 vorhandene Membranschicht 4 soll einerseits Lithiumionen leitend sein, andererseits aber hinreichend stabil, damit bei der Be- schichtung und dem späteren Betrieb die Membranschicht nicht beschädigt wird. Außerdem muss die Membranschicht 4 hinreichend temperaturstabil sein, um ihre mechanischen und elektrischen Eigenschaften beizubehalten, wenn sich die Zelle im Betrieb erwärmt. Wie eingangs ausgeführt, ist dabei der Ladevorgang der kritischere Vorgang, weil der Lade- vorgang ein exothermer Vorgang ist, so dass sich die Verlustwärme und die entstehende Wärme beim chemischen Prozess addieren. Beim Entladevorgang hingegen handelt es sich um einen exothermen chemischen Vorgang, womit die elektrische Verlustwärme zum Teil im exothermen Vorgang aufgebraucht wird, was dazu beiträgt, bei gleichem Strom die Temperatur der Zelle beim Entladevorgang niedriger zu halten.The existing between the anode 2 and the cathode 3 Membrane layer 4 should on the one hand be conductive of lithium ions, but on the other hand should be sufficiently stable so that the membrane layer is not damaged during coating and subsequent operation. In addition, the membrane layer 4 must be sufficiently temperature stable to maintain its mechanical and electrical properties as the cell heats up during operation. As stated above, the charging process is the more critical process, because the charging process is an exothermic process, so that the heat loss and the resulting heat in the chemical process add up. On the other hand, the discharge process is an exothermic chemical process, with which the electrical waste heat is used up in part in the exothermic process, which helps to keep the temperature of the cell lower during the discharge process at the same current.
Unter Lithiumionen leitend versteht der Fachmann eine Membrane, die vereinfacht gesagt, wie ein Sieb arbeitet und lediglich Lithiumionen nicht aber andere Ionen passieren lässt .The person skilled in the art understands the term "lithium ion conductive" to mean a membrane which, in simple terms, works like a sieve and only allows lithium ions to pass other ions.
Auf die Theorie der Lithiumselle soll hier nicht weiter eingegangen werden. Die elektrophysikali sehen Vorgänge, die in der Zelle ablaufen, sind dem Fachmann bekannt und brauchen hier nicht weiter erläutert zu werden.The theory of lithium cell will not be discussed here. The elektrophysikali see processes that occur in the cell are known in the art and need not be further explained here.
Die Membranschicht 2 ist zweilagig und setzt sich aus einer dünnen Lage 11 und einer dickeren Lage 12 zusammen. Die dünne Lage 11 hat eine Stärke zwischen 5 μm und 20 μtn, während die dickere Lage eine Stärke zwischen 10 und 20 μm hat. Die dicke Lage 12 wird für den Herstellungsprozess der Lithiumzelle benutzt und soll bei dem weiteren Herstellungsprozess die dünnere Lage 11 vor einer Beschädigung schützen. Die dickere Lage 12 ist deswegen "porös", d. h. sie hat Durchlässe, die nicht nur Lithiumionen passieren lassen würden.The membrane layer 2 is double-layered and is composed of a thin layer 11 and a thicker layer 12. The thin layer 11 has a thickness of between 5 μm and 20 μm, while the thick layer has a thickness of between 10 and 20 μm. The thick layer 12 is used for the manufacturing process of the lithium cell and should in the further manufacturing process, the thinner layer 11 from damage protect. The thicker layer 12 is therefore "porous", ie it has passages that would not only allow lithium ions to pass through.
Die dicke Lage 12 kann beispielsweise aus einer PoIy- sulfonfolie bestehen. Eine Polysulfonfolie wäre an sich nicht porös. Um sie porös zu bekommen wird sie nach dem Herstellungsprozess gereckt. Hierdurch entstehen die gewünschten durchgehenden Öffnungen. Anschließend wird die so erhaltene Folie beispielsweise durch Kalandrieren im Vakuum auf die dünne Lage 12 aufgebracht.The thick layer 12 may, for example, consist of a poly sulfone film. A polysulfone film would not be porous per se. To get it porous, it is stretched after the manufacturing process. This creates the desired through openings. Subsequently, the film thus obtained is applied, for example by calendering in a vacuum on the thin layer 12.
Die für die Funktion der Lithiumzelle 1 wichtige Schicht 11 hat eine Stärke von 2..5 μm. Das Material für die Schicht 12 kann Polysulfon, Polybenzimidazol oder PoIy- phosphazen sein. Dieses Material ist an sich nach dem Aufbringen auf die Schicht β nicht Lithiumionen leitend. Um die gewünschte lonenleitfähigkeit zu erzeugen, wird die erzeugte Schicht mit Lithiumionen oder Lithiumatomen beschossen. Hierdurch dringen die Lithiumionen oder -atome in die Schicht 11 ein und erzeugen dort die gewünschten Kanäle 13. Es ist nicht erforderlich, dass die Kanäle 13 bis zu der Schicht 6 durchgebrochen werden, es genügt, wenn die Lithiumatome wie bei 14 dargestellt, in dem sackförmigen Kanal 13 stecken bleiben. Der Abstand zwischen dem sackförmigen Ende des Kanals 13 und der Schicht 6 sollte zwischen 10 und 20 nm liegen. Ein anschließender Formierungsvorgang würde die Lithiumionen vollständig durch das Material der Schicht 11 hindurch treiben.The important for the function of the lithium cell 1 layer 11 has a thickness of 2..5 microns. The material for the layer 12 may be polysulfone, polybenzimidazole or polyphosphazene. This material, in itself, after being applied to the layer β, does not conduct lithium ions. In order to produce the desired ionic conductivity, the layer produced is bombarded with lithium ions or lithium atoms. As a result, the lithium ions or atoms penetrate into the layer 11 and generate the desired channels 13. It is not necessary that the channels 13 are broken through to the layer 6, it is sufficient if the lithium atoms as shown at 14, in the stuck sack-shaped channel 13. The distance between the bag-shaped end of the channel 13 and the layer 6 should be between 10 and 20 nm. Subsequent forming operation would drive lithium ions completely through the material of layer 11.
Die solchermaßen erzeugte Lithiumionen leitende Lage oder Schicht 11 der Membranschichtstruktur 4 wird anschließend mittels der Schicht 12, die wie oben erläutert aufge- baut ist, geschützt.The lithium ion conductive layer or layer 11 of the membrane layer structure 4 produced in this way is subsequently heated by means of the layer 12, which is formed as explained above. is build, protected.
Die oben erwähnten Grundmaterialien für die Lage 11 der Membranschicht haben allesamt eine Gasumwandlungstemperatur, die über 150 0C liegt, so dass der einwandfreie Betrieb der Lithiumzelle auch noch bei höheren Temperaturen gewährleistet ist. Die erfindungsgemäß hergestellte Lithiumzelle gestattet somit eine höhere Arbeitstemperatur als die nach dem Stand der Technik aufgebauten Lithiumzellen mit PEO. Die erfindungsgemäßen Akkus können entsprechend sowohl beim' Laden als auch beim Entladen mit größeren Strömen belastet werden.The above-mentioned base materials for the layer 11 of the membrane layer all have a gas transition temperature that is above 150 0 C, so that the proper operation of the lithium cell is guaranteed even at higher temperatures. The lithium cell produced according to the invention thus allows a higher operating temperature than the lithium cells constructed with the prior art with PEO. The batteries according to the invention can be charged correspondingly both during ' loading and unloading with larger currents.
Darüber hinaus zeichnen sich die neuen Lithiumakkus durch einen geringeren Innenwiderstand aus, da die "isolierende" Membran zwischen der Anode und Kathode dünner ist als nach dem Stand der Technik. Die Dicke der Membran hat einen Einfluss auf den Innenwiderstand. Je geringer die Dicke ist, umso kleiner ist auch der Innenwiderstand der Zelle, was wiederum dazu beiträgt, die Verlustwärme beim Laden gering zu halten.In addition, the new lithium batteries are characterized by a lower internal resistance, since the "insulating" membrane between the anode and cathode is thinner than in the prior art. The thickness of the membrane has an influence on the internal resistance. The smaller the thickness, the smaller the internal resistance of the cell, which in turn helps to minimize the heat loss during charging.
Die Lithiuπύonen leitende Lage 11 der Membranschicht 4 kann auch erzeugt werden, indem beispielsweise das oben erwähnte Material unter Zusatz von Stoffen, die aus der Gruppe Li3PO4, Li3P oder Siliziumnanopartikel ausgewählt ist unter Hochdruck auf die Schicht 4 aufgesprüht wird. Die gewünschte Polymerisation erfolgt durch Einwirkung eines Hochfrequenzplasmas, auf das aufgesprühte Material. Die eingebetteten Moleküle sorgen später für die gewünschte Kanalbildung, durch die die Lithiumionen hindurch wandern können. Ein Verfahren zum Hochdruck spühen ist z.B. in der DE 10 2008 047 955 beschrieben. Auf diese Vorveröfentli- chung wird hier Bezug genommen um unnötige Wiederholungen zu vermeinden.The lithiuπύonen conductive layer 11 of the membrane layer 4 can also be produced, for example, by spraying the above-mentioned material with the addition of substances selected from the group Li 3 PO 4 , Li 3 P or silicon nanoparticles under high pressure on the layer 4. The desired polymerization is carried out by the action of a high frequency plasma, on the sprayed material. The embedded molecules later provide the desired channeling that allows the lithium ions to travel through. A method for high pressure annealing is described for example in DE 10 2008 047 955. On this preliminary publication It is referred to here to avoid unnecessary repetition.
Eine weitere Möglichkeit, die Ionen leitende Lage 11 der Membranschicht 4 zu erzeugen, besteht darin einen verlinkten Gelelektrolyten einzusetzen, der aus sternförmig oder linear geformten Polyeterketten besteht. Dieser Stoff bildet ein mechanisches Gerüst, das auch bei Temperaturen über 150 0C mechanisch hinreichend fest ist. Die Zwischenräume in dem Gerüst werden durch PEO gefüllt, das von Haus aus Lithiumionen leitend ist. Andererseits verhindert das eingebettete PEO den Durchtritt anderer Atome, so dass eine Membranschicht 4 erzeugt wird, die lediglich Lithiumionen leitend ist, und zwar auch bei Temperaturen oberhalb 150 0C und somit bei einer Temperatur, die oberhalb des Gasumwandlungspunktes von PEO. Das vorhandene Gerüst aus dem GeI- elektrolyten verhindert, dass das verflüssigte PEO lokal verschwindet, und dort ein Kurzschluss zwischen der Anode und der Kathode entstehen könnte.Another way to produce the ion-conducting layer 11 of the membrane layer 4 is to use a linked gel electrolyte consisting of star-shaped or linearly shaped polyeteketten. This material forms a mechanical scaffolding that is mechanically sufficiently strong even at temperatures above 150 0C. The interstices in the framework are filled by PEO, which is home-made by lithium ions. On the other hand, the embedded PEO prevents the passage of other atoms, so that a membrane layer 4 is generated, which is only lithium ions conductive, even at temperatures above 150 0 C and thus at a temperature above the gas transition point of PEO. The existing scaffold of the gel electrolyte prevents the liquefied PEO from disappearing locally and could cause a short circuit between the anode and the cathode.
Eine weitere Möglichkeit die gewünschte Lithiumionen leitende Lage 11 zu erzeugen, sieht vor eine Membran zu erzeugen, indem eine Sohl-Gelschicht abgeschieden wird. Diese wird aus den Stoffen Polybenimidazol oder PoIy- phosphazen in Kombination mit Zr02-Partikeln ausgewählt. Dieses Material wird im Spinn- oder im Dip-Coating-Verfah- ren aufgetragen und anschließend polymerisiert . Die eingebetteten Zirkondioxid-Moleküle sorgen dafür, dass die entsprechende Lithiumionenleitfähigkeit entsteht.Another way to produce the desired lithium ion conductive layer 11 is to create a membrane by depositing a saline gel layer. This is selected from the substances polybenimidazole or polyphosphazene in combination with ZrO 2 particles. This material is applied by spin coating or dip coating and then polymerized. The embedded zirconium dioxide molecules ensure that the corresponding lithium ion conductivity arises.
Ein Lithium-Akku enthält eine Anoden- und eine Kathodenstruktur, die voneinander durch eine Membranstruktur getrennt sind. Zu der Membranstruktur gehört eine Lage, die lediglich Lithiumionen leitend ist und die sich durch die Eigenschaft auszeichnet oberhalb von der Temperatur 15O1 0C mechanisch hinreichend fest zu sein, um einen lokalen Kurz- schluss zwischen der Anoden- und der Kathodenstruktur zu verhindern. A lithium battery contains an anode and a cathode structure separated from each other by a membrane structure. The membrane structure includes a layer that only lithium ions is conductive and is characterized by the property above the temperature 15O 1 0 C mechanically sufficiently firm to prevent a local short circuit between the anode and the cathode structure.

Claims

Patentansprüche claims
1. Lithiumionen-Akku (1)1. Lithium ion battery (1)
- mit einer Kathode (3), die ein metallisch leitendes Substrat (5) und eine auf dem Substrat (5) befindliche polykristalline Schicht (6) aufweist,comprising a cathode (3) having a metallically conductive substrate (5) and a polycrystalline layer (6) located on the substrate (5),
- mit einer Ionen leitenden Membranstruktur (4), die wenigstens eine Lithium leitende Schicht (11) aufweist,with an ion-conducting membrane structure (4) which has at least one lithium-conducting layer (11),
- mit einer Anode (2), die sich aus einer polykristallinen Schicht (7) und einer metallisch leitenden Schicht (8) zusammensetzt, wobei die polykristalline Schicht (7) der Membranstruktur (4) zugekehrt ist, dadurch gekennzeichnet, dass die Lithium leitende Schicht (11) eine dünne, gasdichte Polymerfolie ist, die derart physikalisch behandelt ist, dass durch einen Beschuss mit Lithiumionen oder Lithiumatomen in der Lithium leitenden Schicht (11 ) Kanäle und/oder Lithiumionen oder Lithiumatome eingebracht sind.- With an anode (2), which consists of a polycrystalline layer (7) and a metallically conductive layer (8), wherein the polycrystalline layer (7) of the membrane structure (4) faces, characterized in that the lithium-conducting layer (11) is a thin, gas-tight polymer film which is physically treated such that channels and / or lithium ions or lithium atoms are introduced by bombardment with lithium ions or lithium atoms in the lithium-conducting layer (11).
2. Lithiumionen-Akku nach Anspruch 1 , dadurch gekennzeichnet, dass der Abstand zwischen einem eingeschossenen Lithiumatom und der an die Lithium leitende Schicht (11) angrenzenden Anode (2), Kathode (3) oder weiteren Schicht nicht größer als 20 nm ist.Second lithium-ion battery according to claim 1, characterized in that the distance between an injected lithium atom and the to the lithium-conducting layer (11) adjacent anode (2), cathode (3) or further layer is not greater than 20 nm.
3. Lithiumionen-Akku nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Lithium leitende Schicht (11) eine Stärke von 2 bis 19 μm, insbesondere von 2 bis 5 μm aufweist.3. lithium ion battery according to claim 1 or 2, characterized in that the lithium-conducting layer (11) has a thickness of 2 to 19 .mu.m, in particular from 2 to 5 microns.
4. Lithiumionen-Akku nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Ionen leitenden Membranstruktur (4), eine zweite Schicht (12) aufweist, die porös ist.4. Lithium-ion battery according to one of claims 1 to 3, characterized in that the ion-conducting membrane structure (4), a second layer (12) which is porous.
5. Lithiumionen-Akku nach Anspruch 4, dadurch gekennzeichnet, dass die Lithium leitende Schicht (11) dünner als die zweite Schicht (12) ist. 5. Lithium-ion battery according to claim 4, characterized in that the lithium-conducting layer (11) is thinner than the second layer (12).
6. Lithiumionen-Akku nach einem der Ansprüche 4 oder 5, dadurch gekennzeichnet, dass die zweite Schicht eine Stärke zwischen 10 und 20 μm aufweist.6. lithium ion battery according to one of claims 4 or 5, characterized in that the second layer has a thickness between 10 and 20 microns.
7. Lithiumionen-Akku nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das metallisch leitende Substrat (5) eine Nickel- oder eine Edelstahlschicht ist.7. Lithium-ion battery according to one of claims 1 to 6, characterized in that the metallically conductive substrate (5) is a nickel or a stainless steel layer.
8. Lithiumionen-Akku nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass wenigstens eine der polykristallinen Schichten (6, 7) eine nanokristalline Schicht ist.8. lithium ion battery according to one of claims 1 to 7, characterized in that at least one of the polycrystalline layers (6, 7) is a nanocrystalline layer.
9. Lithiumionen-Akku nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die polykristalline Schicht (6) der Kathode (3) aus den Stoffen MnO2, CoO2 oder NiMn ausgewählt ist.9. lithium ion battery according to one of claims 1 to 8, characterized in that the polycrystalline layer (6) of the cathode (3) is selected from the materials MnO 2 , CoO 2 or NiMn.
10. Lithiumionen-Akku nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Ionen leitenden Membranstruktur (4) aus der Gruppe der Stoffe Polyetherketon, Polysulfon, Polyimid, Polyethersulfon, Polybenzimidazol oder Polyphosphazenpolymer ausgewählt ist.10. Lithium ion battery according to one of claims 1 to 9, characterized in that the ion-conducting membrane structure (4) is selected from the group of substances polyether ketone, polysulfone, polyimide, polyethersulfone, polybenzimidazole or polyphosphazene polymer.
11. Lithiumionen-Akku nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass die polykristalline Schicht (7) der Anode (2) aus den Stoffen C1 Si1 LiAI, LiC oder LiNi ausgewählt ist. 11. Lithium ion battery according to one of claims 1 to 10, characterized in that the polycrystalline layer (7) of the anode (2) is selected from the substances C 1 Si 1 LiAl, LiC or LiNi.
12. Lithiumionen-Akku nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass die Ionen leitende Membranstruktur (4) Polyethylenoxid aufweist.12. Lithium-ion battery according to one of claims 1 to 11, characterized in that the ion-conducting membrane structure (4) comprises polyethylene oxide.
13. Lithiumionen-Akku nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass die Lithium leitende Schicht (11) kovalent verlinkte Gel-Elektrolyten enthält, die aus sternförmig oder linear geformten Polymerketten bestehen, in denen Lithiumionen leitendes Material eingebettet ist.13. Lithium-ion battery according to one of claims 1 to 12, characterized in that the lithium-conducting layer (11) contains covalently linked gel electrolytes which consist of star-shaped or linearly shaped polymer chains in which lithium-ion conducting material is embedded.
14. Verfahren zur Herstellung eines Lithiumionen-Akku (1)14. Method for producing a lithium ion battery (1)
- mit einer Kathode (3), die ein metallisch leitendes Substrat (5) und eine auf dem Substrat (5) befindliche polykristalline Schicht (6) aufweist,comprising a cathode (3) having a metallically conductive substrate (5) and a polycrystalline layer (6) located on the substrate (5),
- mit einer Ionen leitenden Membranstruktur (4), die wenigstens eine Lithium leitende Schicht (11) aufweist,with an ion-conducting membrane structure (4) which has at least one lithium-conducting layer (11),
- mit einer Anode (2), die sich aus einer polykristallinen Schicht (7) und einer metallisch leitenden Schicht (8) zusammensetzt, wobei die polykristalline Schicht (7) der Membranstruktur (4) zugekehrt ist, dadurch gekennzeichnet, dass die Lithium leitende Schicht (11) als dünne, gasdichte Polymerfolie auf eine zweite Schicht (12) der Membranstruktur (4) aufgebracht und anschließend mit Lithiumionen oder Lithiumatomen beschossen wird.- With an anode (2), which consists of a polycrystalline layer (7) and a metallically conductive layer (8), wherein the polycrystalline layer (7) of the membrane structure (4) faces, characterized in that the lithium-conducting layer (11) is applied as a thin, gas-tight polymer film on a second layer (12) of the membrane structure (4) and then bombarded with lithium ions or lithium atoms.
15. Verfahren nach Anspruch 14, dadurch gekennzeichnet, dass die Lithium leitende Schicht (11) als dünne, gasdichte Polymerfolie auf die zweite Schicht (12) der Membranstruktur (4) abgeschieden wird.15. The method according to claim 14, characterized in that the lithium-conducting layer (11) is deposited as a thin, gas-tight polymer film on the second layer (12) of the membrane structure (4).
16. Verfahren nach Anspruch 15, dass die Lithium leitende Schicht (11) mittels Dip- oder Spin-Coating auf die zweite Schicht (12) der Membranstruktur (4) abgeschieden wird. 16. The method according to claim 15, that the lithium-conducting layer (11) by means of dip or spin coating on the second layer (12) of the membrane structure (4) is deposited.
17. Verfahren nach Anspruch 14, dadurch gekennzeichnet, dass die Lithium leitende Schicht (11) auf die zweite Schicht (12) der Membranstruktur (4) mittels Hochdruckverdüsung aufgesprüht wird.17. The method according to claim 14, characterized in that the lithium-conducting layer (11) is sprayed onto the second layer (12) of the membrane structure (4) by means of high-pressure atomization.
18. Verfahren nach Anspruch 17, dadurch gekennzeichnet, dass die Lithium leitende Schicht (11) auf die zweite Schicht (12) der Membranstruktur (4) unter Zusatz von aus der Gruppe Li3Po4, Li3P, und Siliziumpartikeln ausgewählten Stoffen aufgesprüht wird.18. The method according to claim 17, characterized in that the lithium-conducting layer (11) sprayed on the second layer (12) of the membrane structure (4) with the addition of selected from the group Li 3 Po 4 , Li 3 P, and silicon particles becomes.
19. Verfahren nach einem der Ansprüche 14 bis 18, dadurch gekennzeichnet, dass die Lithium leitende Schicht (11) auf die Anode (2) oder die Kathode aufgebracht wird.19. The method according to any one of claims 14 to 18, characterized in that the lithium-conducting layer (11) is applied to the anode (2) or the cathode.
20. Verfahren nach einem der Ansprüche 14 bis 19, dadurch gekennzeichnet, dass die Lithium leitende Schicht (11) auf die zweite Schicht (12) der Membranstruktur (4) als Sol-Gel-Schicht abgeschieden wird, die Polybenzimidazol oder Polyphosphazen in Kombination mit ZrtVPartikeln aufweist. 20. The method according to any one of claims 14 to 19, characterized in that the lithium-conducting layer (11) is deposited on the second layer (12) of the membrane structure (4) as a sol-gel layer, the polybenzimidazole or polyphosphazene in combination with ZrtVPartikeln has.
EP09736241A 2008-10-20 2009-10-19 Lithium ion battery Not-in-force EP2338190B1 (en)

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DE102008054187.7A DE102008054187B4 (en) 2008-10-20 2008-10-31 Lithium ion battery and process for producing a lithium ion battery
PCT/EP2009/063682 WO2010046346A1 (en) 2008-10-20 2009-10-19 Lithium ion battery

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DE102008054187B4 (en) 2014-08-21
US20120021297A1 (en) 2012-01-26
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DE102008054187A1 (en) 2010-04-22
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JP2012506130A (en) 2012-03-08
EP2338190B1 (en) 2013-02-13
KR20110071115A (en) 2011-06-28

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